This work reports the effects of solvent properties, solvent system, electrostatic field

Iranian Polymer Journal 15 (4), 2006, 341-354 Available online at: http://journal.ippi.ac.ir Effects of Solvent Properties, Solvent System, Electrostatic Field Strength, and Inorganic Salt Addition on Electrospun Polystyrene Fibres Jiranun Manee-in 1, Manit Nithitanakul 1, and Pitt Supaphol 1,2* (1) The Petroleum and Petrochemical College, Chulalongkorn University, Soi Chula 12, Phyathai Road, Pathumwan, Bangkok-10330, Thailand (2) Conductive and Electroactive Polymers Research Unit, Chulalongkorn University, Soi Chula 12, Phyathai Road, Pathumwan, Bangkok-10330, Thailand ABSTRACT Received 14 February 2006; accepted 22 March 2006 This work reports the effects of solvent properties, solvent system, electrostatic field strength, and inorganic salt addition on electro-spinnability of the as-prepared polystyrene (PS) solutions and morphological appearance and/or size of the resulting fibres. The single solvents were 1,2-dichloroethane (DCE), dimethylformamide (DMF), ethylacetate (EA), and methylethylketone (MEK), while the mixed solvents were DMF/DCE, DMF/EA, and DMF/MEK at a fixed volumetric ratio of 75/25. The PS solution 10% (w/v) in DMF was found to exhibit the highest electro-spinnability, followed by its solutions in DCE, MEK, and EA, respectively. Generally, electrospinning of 10% (w/v) PS solution resulted in the formation of the beaded fibres, while electrospinning of 20 and 30% (w/v) PS solutions only resulted in the formation of smooth fibres. The size of the obtained fibres was found to increase with an increase in both the electrostatic field strength and the concentration of the PS solutions. Interestingly, the presence of DCE, EA, and MEK as the minor solvent (at 25 vol%) in a mixture with DMF reduced the size of the obtained fibres. Finally, incorporation of LiCl and KCl to modify the conductivity of the PS solutions caused the size of the fibres to increase appreciably. Key Words: electrospinning; ultrafine fibres; polystyrene; morphology; solvent. (*) To whom correspondence should be addressed. E-mail: pitt.s@chula.ac.th INTRODUCTION When diameters of polymeric fibres decreases from micrometers down to sub-micrometers or even nanometers, there appear to be several interesting characteristics such as high surface area to volume or mass ratio, vast possibility for surface functionalization, and improved mechanical performance due to an improvement in structural organization. These interesting properties make ultrafine electrospun polymeric fibres excellent candidates for many important applications, some of which are fil-

Effects of Solvent Properties, Solvent System... Manee-in J. et al. tration, reinforcing materials, wound dressing, tissue scaffolding, releasing vehicles of drugs, and so on so forth [1]. The electrospinning process seems to be a simple method that can be developed for mass production of continuous ultrafine fibres from materials of diverse origins, e.g. polymers, ceramics, etc. Some advantages of the process are simple tooling, cost-effectiveness, and ability for producing fibre mats with certain degrees of control over the alignment of and pore sizes between depositing fibres. Consequently, the process has received much interest from scientists and technologists alike, with the number of publications in the open literature increasing from about 30 in 2001 to about 250 in 2005 [2]. Set-up of the electrospinning process is traditionally simple. The three major components are a high-voltage power supply, a container for a polymer liquid with a small opening, and a conductive collector plate [1]. The emitting electrode of the power supply was connected to the polymer liquid, while the grounding one was connected to the collector plate to complete the electrical circuit. At a critical applied electrostatic field strength, the repulsion of mutual charges within the polymer liquid and the electrode destabilizes the partially spherical pendant drop into a conical shape (i.e., Taylor s cone) at the tip of a conductive nozzle connected to the small opening of the container. Further increase in the electrostatic field strength causes an electrically-charged stream of the polymer liquid (i.e., charged jet) be ejected from the apex of the cone. The jet travels in a straight trajectory for only a short distance before undergoing a bending instability that causes the conical looping trajectory with its apex locating at the onset point of the bending instability [3]. Finally, the jet rests on the collector plate as a nonwoven fibre mat [3-5]. In the electrospinning of a polymer solution, a number of parameters affecting the morphology of the obtained fibres are (1) solution properties (e.g., concentration, viscosity, conductivity, and surface tension), (2) process factors (e.g., applied potential, collection distance, emitting electrode polarity, and feed rate), and (3) ambient parameters (e.g., temperature, relative humidity, and velocity of the surrounding air in the spinning chamber) [5,6]. Baumgarten [7] was among the first group of researchers carried out a detailed study on the effects of some solution properties (e.g., concentration, viscosity, etc.) and process factors (e.g., applied potential, solution feed rate, etc.) parameters on morphology and diameters of the electrospun polyacrylonitrile (PAN) fibres. He found that an increase in the solution viscosity is responsible for the observed increase in the diameters of the as-spun PAN fibres, while an increase in the solution feed rate did not affect much the diameters of the fibres. Wannatong et al. [8] investigated the effect of six solvents (i.e., acetic acid, acetonitrile, m-cresol, toluene, tetrahydrofuran (THF), and dimethylformamide (DMF)) on morphology and size of the electrospun polystyrene (PS) fibres. Fibre diameters decreased with increasing density and boiling point of the solvents. A large difference between the solubility parameters of PS and the solvent was responsible for the observed bead-on-string morphology. Productivity of the fibres increased with increasing dielectric constant and dipole moment of the solvents. In a subsequent work, Jarusuwannapoom et al. [9] reported a more systematic study on the effects of eighteen solvents and their properties on electro-spinnability of PS solutions and appearance of the as-spun fibres. Among the eighteen solvents (i.e., benzene, t-butylacetate, carbontetrachloride, chlorobenzene, chloroform, cyclohexane, decahydronaphthalene (decalin), 1,2- dichloroethane (DCE), DMF, 1,4-dioxane, ethylacetate (EA), ethylbenzene, hexane, methylethylketone (MEK), nitrobenzene, THF, 1,2,3,4-tetrahydronaphthalene (tetralin), and toluene) only the PS solutions in DCE, DMF, EA, MEK, and THF produced fibres with high enough productivity. The main objective of this work was to perform a systematic study on the effect of solvent system (only focussing on DCE, DMF, EA, and MEK), applied electrostatic field strength, and ionic salt addition on morphology and/or size of the electrospun PS fibres. The as-spun PS fibres were characterized mainly by scanning electron microscopy (SEM). EXPERIMENTAL Materials and Method The polystyrene (PS) resin (Mw 3.0 10 5 Da and polydispersity 2.5) was a commercial, general pur- 342 Iranian Polymer Journal / Volume 15 Number 4 (2006)

Manee-in J. et al. Effects of Solvent Properties, Solvent System... pose grade (Styron 685D; Dow Plastic, USA). The four solvents used were 1,2-dichloroethane [DCE; Labscan (Asia), Thailand], N,N-dimethylformamide [DMF; Labscan (Asia), Thailand], ethylacetate [EA; Labscan (Asia), Thailand], and methylethylketone [MEK; Carlo Erba, Italy]. Some important properties of these solvents are summarized in Table 1. Lithium chloride (LiCl) and potassium chloride (KCl) were purchased from Ajax Chemicals, Australia. All chemicals were of analytical grade and used as received. The spinning solutions were prepared in either single or mixed solvent system. For the single solvent system, PS pellets were dissolved in DCE, DMF, EA, or MEK, while, for the mixed solvent system, PS pellets were dissolved in a mixed solvent of DMF/DCE, DMF/EA, or DMF/MEK [at 75/25 (v/v)]. For the single solvent system, the concentration of the as-prepared PS solutions was 10, 20, or 30% (w/v), while, for the mixed solvent system, the concentration of the as-prepared PS solutions was fixed at 30% (w/v). Some of the solution properties, i.e., viscosity, conductivity, and surface tension were measured at ambient condition (i.e., 25 ± 1 o C) by a Brookfield DV-III programmable viscometer, an Orion 160 conductivity meter, and a Kru.. ss DSA10 Mk2 drop shape analyzer, respectively. To investigate the effect of inorganic salt addition, about 1% (w/v) of LiCl or KCl was dissolved in the 30% (w/v) PS solutions in DMF, DMF/DCE, DMF/EA, or DMF/MEK. The volumetric ratio of the mixed solvents was 75/25. In the electrospinning set-up, a glass syringe was used to stock each of the as-prepared PS solutions. A 1cm long blunt-end stainless-steel gauge 18 (OD = 1.2 mm) needle was used as the nozzle. Both the needle and the syringe were tilted about 45 o from a horizontal baseline to maintain constant presence of a droplet at the tip of the needle. The feed rate of the solution was controlled by pressurized nitrogen gas through a flow meter. A piece of thick aluminium (Al) sheet was used as a screen collector. A Gamma High Voltage Research D-ES30PN/M692 power supply was used to charge the PS solution by connecting the emitting electrode to the needle and the ground to the screen collector. Unless otherwise noted, the applied electrostatic field strength was varied (i.e., 1:1, 2:1, or 3:1 kv/cm), either by fixing the collection distance (i.e., 7 kv/7 cm, 14 kv/7 cm, or 21 kv/7 cm) or the applied potential (i.e., 25 kv/25 cm, 25 kv/12.5 cm, or 25 kv/8.3 cm). In all cases, the polarity of the emitting electrode was positive and the collection time was 15 s. Morphological appearance and size of the as-spun PS fibres were investigated by means of a JEOL JSM- 5200 scanning electron microscope (SEM). Each specimen was coated with a thin layer of gold using a JEOL JFC-1100E ion sputtering device prior to observation under SEM. The average size of the as-spun fibres was calculated from at least 80 readings from multiple SEM images for each specimen. The electro-spinnability of the spinning solutions or the productivity of the resulting as-spun PS fibres was quantified by the amount of fibres observed on SEM images obtained for each spinning condition. RESULTS AND DISCUSSION Effect of Solvent Properties on Productivity of Asspun Fibres In order to study the effect of solvent on electrospinnability of the resulting PS solutions, the selected SEM images of the as-spun fibres were analyzed which were taken from 10% (w/v) PS solutions in each of the single solvents. In this case, the electro-spinnability was assessed by the amount of the as-spun fibres that were collected on a unit area. Practically, it was quan- Table 1. Some properties of solvents used in this work. Solvent Chemical formula Molecular weight (g/mol) Boiling point ( o C) 83.5 Density (g/cm 3 ) 1.24 Dipole moment (Debye) Dielectric Solubility parameter constant (MPa)1/2 1,2-dichloroethane (DCE) ClCH 2 CH 2 Cl 99.0 2.94 10.2 20.2 Dimethylformamide (DMF) (CH 3 ) 2 NCHO 73.1 153.0 0.94 3.82 38.3 24.0 Ethylacetate (EA) CH 3 COOCH 2 CH 3 88.1 77.1 0.89 1.78 6.0 18.3 Methylethylketone (MEK) CH 3 CH 2 COCH 3 72.1 79.6 0.79 2.76 18.5 18.8 Iranian Polymer Journal / Volume 15 Number 4 (2006) 343

Effects of Solvent Properties, Solvent System... Manee-in J. et al. (a) (b) (c) (d) (e) (f) Figure 1. The effects of (a) molecular weight, (b) boiling point, (c) density, (d) dipole moment, (e) dielectric constant of the solvents, and (f) difference in the solubility of the solvents and the PS solute on electro-spinnability of 10% (w/v) PS solutions in various solvents. The applied electrostatic field strength was 25 kv/12.5 cm. 344 Iranian Polymer Journal / Volume 15 Number 4 (2006)

Manee-in J. et al. Effects of Solvent Properties, Solvent System... tified by the number of pixels of the as-spun fibres on an SEM image divided by the total number of pixels of a viewing area, using the Adobe Photoshop 7.0 image analytical software. Based on such analyses, the electro-spinnability of the PS solution in DMF was found to be the best, followed by its solution in DCE, MEK, and EA, respectively, which is agreed well with a previous report [9]. The effect of solvent on electro-spinnability of the PS solutions in DMF, DCE, MEK, and EA can be discussed further against some influencing properties of the solvents. Figure 1 shows overlay plots of the electro-spinnability and some property values of the solvents (i.e., molecular weight, boiling point, density, dipole moment, dielectric constant, and difference in the solubility parameters between that of the solvent and the PS solute molecules), while Figure 2 illustrates overlay plots of the electro-spinnability and some property values of the resulting solutions (i.e., viscosity, surface tension, and conductivity). Obviously, electrospinnability of the PS solutions or productivity of the obtained as-spun fibres correlated well with the boiling point, dipole moment, and dielectric constant of the solvents, and the difference between the solubility parameters of the solvent and the solute, as well as with the viscosity of the resulting PS solutions. Specifically, the productivity of the as-spun fibres decreased with a decrease in the boiling point, dipole moment, and dielectric constant of the solvents, the difference between the solubility parameters of the solvent and the solute, and viscosity of the solutions. Table 2 summarizes the viscosity, surface tension, and conductivity of the as-prepared PS solutions in DMF, DCE, MEK, and EA, separatly. The property value of the pure solvents was also listed for comparison. Based on the obtained results, the electro-spinnability of the as-prepared solutions did not correlate well with both the conductivity and the surface tension of the solutions. Wutticharoenmongkol et al. [10] showed that the addition of a type of salt which increase the conductivity of the solutions improved the electro-spinnability of the resulting solutions greatly, but such an observation did not hold in the case of the conductivity of the solutions, excepted for the PS solution in DMF, which showed the highest conductivity among those investigated, exhibiting the highest productivity of the as-spun fibres (Figure 2c). (a) (b) (c) Figure 2. The effects of (a) viscosity, (b) surface tension, and (c) conductivity on electro-spinnability of 10% (w/v) PS solutions in various solvents. The applied electrostatic field strength was 25 kv/12.5 cm. Iranian Polymer Journal / Volume 15 Number 4 (2006) 345

Effects of Solvent Properties, Solvent System... Manee-in J. et al. Effect of Single Solvent System DCE Was able to dissolve PS pellets to form a clear solution within two days. The viscosity of 10, 20, and 30% (w/v) PS solutions in DCE increased from that of the pure solvent (i.e., 0.73 cp) to about 28.8, 171, and 1570 cp, respectively (Table 2). The surface tension increased slightly from that of the pure solvent (i.e., 32.5 mn/m 2 ) to about 33.2, 33.3, and 33.9 mn/m 2, respectively (Table 2). Finally, the conductivity decreased from that of the pure solvent (i.e., 0.70 µs/cm) to about 0.25, 0.21, and 0.20 µs/cm, respectively (Table 2). Electrospinning of the PS solutions in DCE was easy, most likely as the results of the relatively high dipole moment (i.e., 2.94 Debye; Table 1) and the relatively high dielectric constant (i.e., 10.2; Table 1) of the solvent. DMF was able to dissolve PS pellets to form a clear solution within only 6 h. The viscosity of 10, 20, and 30% (w/v) PS solutions in DMF increased from that of the pure solvent (i.e., 0.85 cp) to about 25.4, 217, and 1020 cp, respectively (Table 2). The surface tension increased very slightly from that of the pure solvent (i.e., 35.5 mn/m 2 ) (Table 2). Finally, the conductivity decreased drastically from that of the pure solvent (i.e., 6.72 µs/cm) to about 0.81, 0.82, and 0.88 µs/cm, respectively (Table 2). Electrospinning of the PS solutions in DMF was the easiest among the all solvents investigated in this work, most likely as the results of the very high dipole moment (i.e., 3.82 Debye; Table 1) and the very high dielectric constant (i.e., 38.3; Table 1) of the solvent in comparison with other solvents investigated. EA Was able to dissolve PS pellets to form a clear solution within three days. The viscosity of 10, 20, and 30% (w/v) PS solutions in EA increased from that of the pure solvent (i.e., 0.56 cp) to about 18.4, 186, and 1420 cp, respectively (Table 2). The surface tension decreased very slightly from that of pure solvent (i.e., 24.7 mn/m 2 ) to about 24.2, 23.9, and 23.5 mn/m 2, respectively (Table 2). Finally, the conductivity decreased significantly from that of the pure solvent (i.e., 0.70 µs/cm) to about 0.04 µs/cm, regardless of the concentration (Table 2). Electrospinning of the PS solutions in EA was the worst among the all solvents investigated in this work, most likely as the results of the very low dipole moment (i.e., 1.78 Debye; Table 1) and the very low dielectric constant (i.e., 6.0; Table 1) of the solvent in comparison with other solvents investigated. MEK Was able to dissolve PS pellets to form a clear solution within one day. The viscosity of 10, 20, and 30% (w/v) PS solutions in MEK increased from that of the pure solvent (i.e., 0.56 cp) to 16.8, 158, and 700 cp, respectively (Table 2). The surface tension decreased slightly from that of pure solvent (i.e., 24.4 mn/m 2 ) to about 23.5, 23.1, and 22.9 mn/m 2, respectively (Table 2). Finally, the conductivity decreased moderately from that of the pure solvent (i.e., 0.92 µs/cm) to about 0.45, 0.48, and 0.40 µs/cm, respectively (Table 2). Electrospinning of the PS solutions in MEK was comparable to that of the solutions in DCE, most likely as the results of the relatively high dipole moment (i.e., 2.76 Debye; Table 1) and the relatively high dielectric constant (i.e., 18.5; Table 1) of the solvent. Tables 3 and 4 summarize selected SEM images of as-spun fibres from 10% (w/v) PS solutions in DCE, DMF, EA, and MEK under varying electrostatic field strength for either a fixed applied potential with varying collection distance or a fixed collection distance with varying applied potential. A combination of smooth and beaded fibres was evident in all of the SEM images. Even though increasing the concentration of the PS solutions to 20 and 30% (w/v), respectively, Table 2. Viscosity, surface tension, and conductivity of as-prepared PS solutions in 1,2-dichloroethane, dimethylformamide, ethylacetate, and methylethylketone. Solvent 1,2-Dichloroethane (DCE) Dimethylformamide (DMF) Ethylacetate (EA) Methylethylketone (MEK) Viscosity (cp) Surface tension (mn/m 2 ) Conductivity (µs/cm) 10% 20% Pure solvent (w/v) (w/v) 0.73 28.8 171 1570 0.85 0.56 0.56 25.4 18.4 16.8 217 186 158 30% (w/v) Pure solvent 10% (w/v) 1020 1420 700 32.5 35.5 24.7 24.4 33.2 36.0 24.2 23.5 20% (w/v) 33.3 35.9 23.9 23.1 30% (w/v) Pure solvent 10% (w/v) 33.9 35.7 23.5 22.9 0.70 6.72 0.70 0.92 20% 30% (w/v) (w/v) 0.25 0.21 0.20 0.81 0.04 0.45 0.82 0.04 0.48 0.88 0.05 0.40 346 Iranian Polymer Journal / Volume 15 Number 4 (2006)

Manee-in J. et al. Effects of Solvent Properties, Solvent System... Table 3. Selected scanning electron micrographs (scale bar = 50 µm and magnification 500x) of as-spun fibers from 10% (w/v) PS solutions in 1,2-dichloroethane, dimethylformamide, ethylacetate, and methylethylketone under varying electrostatic field strength (for a fixed applied potential). Solvent Electrostatic field strength 25 kv/25 cm 25 kv/12.5 cm 25kV/8.3cm DCE 1 DMF 2 EA 3 MEK 4 (1) 1,2-dichloroethane; (2) Dimethylformamide; (3) Ethylacetate; (4) Methylethylketone. resulted in the formation of smooth and bead-free fibres (results not shown), the SEM images of the fibres obtained from 10% (w/v) PS solutions were shown here because more information can be obtained through the examination of these images. Table 5 summarizes diameters (or widths) of the as-spun fibres from PS solutions in DCE, DMF, EA, and MEK under various electrostatic field strengths. For beaded fibres, their Iranian Polymer Journal / Volume 15 Number 4 (2006) 347

Effects of Solvent Properties, Solvent System... Manee-in J. et al. Table 4. Selected scanning electron micrographs (scale bar = 50 µm and magnification 500x) of as-spun fibers from 10% (w/v) PS solutions in 1,2-dichloroethane, dimethylformamide, ethylacetate, and methylethylketone under varying electrostatic field strength (for a fixed collection distance). Solvent Electrostatic field strength 7 kv/7 cm 14 kv/7 cm 21 kv/7 cm DCE 1 DMF 2 EA 3 MEK 4 (1) 1,2-dichloroethane; (2) Dimethylformamide; (3) Ethylacetate; (4) Methylethylketone. diameters were measured on the parts without the presence of the beads. According to Tables 3 and 4, for a fixed applied potential of 25 kv, the size of the beads decreased with decreasing collection distance and for a fixed collection distance of 7 cm, the size of the beads decreased with increasing applied potential. These observations directly imply that the size of the beads decreased with increas- 348 Iranian Polymer Journal / Volume 15 Number 4 (2006)

Manee-in J. et al. Effects of Solvent Properties, Solvent System... ing electrostatic field strength. In addition the shape of the beads appeared to be more elongated when electrostatic field strength increased. In addition to the results listed in Table 5, the size of the fibres increased with an increase in both the electrostatic field strength (i.e., a decrease in the collection distance for a fixed applied potential of 25 kv or an increase in the applied potential for a fixed collection distance of 7 cm) and the concentration of the PS solutions. Interestingly, when the size of the fibres exceeded to 8-10 µm, flat ribbon-like fibres were obtained instead of the cross-sectionally round ones. This is in accordance with the previous report [9]. In such cases, the size of the fibres went by their width. Regardless of the spinning conditions, the diameters or widths of the fibres from the PS solutions in DCE ranged between 0.8 and 6.7 µm; those of the fibres from the PS solutions in DMF ranged between 1.3 and 15.7 µm; those of the fibres from the PS solutions in EA ranged between 0.6 and 23.9 µm; and those of the fibres from the PS solutions in MEK ranged between 1.0 and 13.6 µm, respectively (Table 5). It should be emphasized that, despite the implication of the technique that is capable of producing fibres in the nanometer range, the actual sizes of the fibres obtained depend very much on the type of the polymer and the size of the needle used, among many other factors. Solution properties (i.e., viscosity, conductivity, and surface tension) have been shown to have a significant effect on the morphological appearance of the asspun fibres [5]. In order to describe the experimental observations based on these properties, one needs to be familiar with the six types of force that are involved in the electrospinning process [8]. They are 1) body or gravitational force, 2) electrostatic force which carries the charged jet from the needle to the screen collector, 3) coulombic stretching force which tries to push apart adjacent charged species being present within the jet Table 5. Diameters (or widths) of as-spun fibers from PS solutions in 1,2-dichloroethane, dimethylformamide, ethylacetate, and methylethylketone under varying electrostatic field strength for either a fixed applied potential with varying collection distance or a fixed collection distance with varying applied potential. Concentration of PS solution (w/v) Fiber diameters (or widths) (µm) 25 kv/25 (cm) 25 kv/12.5 (cm) 25kV/8.3 (cm) 7 kv/7 (cm) 14 kv/7 (cm) 21 kv/7 (cm) In 1,2-dichloroethane (DCE) 10 1.2 ± 0.3 1.2 ± 0.2 1.4 ± 0.3 0.8 ± 0.2 0.9 ± 0.3 1.1 ± 0.2 20 4.4 ± 2.4 3.1 ± 1.2 3.9 ± 1.7 1.4 ± 0.2 2.6 ± 0.2 4.2 ± 1.3 30 4.8 ± 1.1 5.1 ± 1.2 5.5 ± 1.9 2.5 ± 0.5 5.3 ± 0.6 6.7 ± 1.2 In dimethylformamide (DMF) 10 2.2 ± 0.5 2.4 ± 0.6 2.5 ± 0.5 1.3 ± 0.3 1.6 ± 0.4 2.0 ± 0.5 20 3.0 ± 0.4 3.3 ± 0.6 4.8 ± 0.5 2.5 ± 0.5 3.2 ± 0.7 4.3 ± 0.7 30 7.9 ± 0.6 8.3 ± 1.3 15.7 ± 1.7 5.7 ± 0.7 8.5 ± 0.6 11.5 ± 1.8 In ethylacetate (EA) 10 0.8 ± 0.3 1.0 ± 0.3 1.1 ± 0.3-0.6 ± 0.2 1.3 ± 0.3 20 8.9 ± 2.8 9.7 ± 1.7 21.6 ± 8.5 3.5 ± 0.2 6.9 ± 1.5 7.4 ± 1.1 30 13.2 ± 3.4 21.0 ± 2.9 23.9 ± 4.0 4.5 ± 0.5 8.2 ± 1.6 15.2 ± 2.6 In methylethylketone (MEK) 10 1.3 ± 0.3 1.3 ± 0.3 1.4 ± 0.2 1.0 ± 0.2 1.3 ± 0.3 1.3 ± 0.3 20 4.8 ± 0.9 6.4 ± 1.1 7.3 ± 1.7 3.5 ± 0.5 7.2 ± 2.3 8.2 ± 1.9 30 8.9 ± 1.5 9.2 ± 1.0 11.5 ± 3.5 9.8 ± 1 11.5 ± 1.1 13.6 ± 2.1 Iranian Polymer Journal / Volume 15 Number 4 (2006) 349

Effects of Solvent Properties, Solvent System... Manee-in J. et al. segment and is responsible for the thinning or the stretching of the charged jet during its flight to the target, 4) viscoelastic force which tries to prevent the charged jet from being stretched, 5) surface tension also acts against the stretching of the surface of the charge jet, and 6) drag force from the friction between the charged jet and the surrounding air. At low solution concentrations or low solution viscosities, the viscoelastic force is lower than the coulombic stretching force, causing the charged jet to break up into smaller jets and, with the work of the surface tension, the smaller jets are rounded up to finally form the discrete droplets on the collector. Marginal increase in the solution viscosities causes the charged jet to be able to withstand the coulombic stretching more readily. In such a case, the influence of the surface tension can result in the formation of beaded fibres, a phenomenon described as the axisymmetric instabilities [11]. Zuo et al. [11] demontrated that such instabilities can be suppressed by a decrease in both the surface tension and the feeding rate of the solution and an increase in the electrostatic field strength. The results summarized in Tables 3 and 4 confirmed that increasing the electrostatic field strength decreased the tendency for bead formation. Further increase in the solution viscosities causes the charged jet to be able to withstand the coulombic stretching completely, thus resulting in the formation of bead-free fibres. Further examination of the as-spun products obtained from 10% (w/v) PS solutions in DMF and EA revealed the significance of the solution properties on the morphological appearance of the as-spun fibres. According to Table 2, all of the property values of the PS solution in DMF were greater than those of the PS solution in EA. Since the conductivity of a solution relates to the amount of the charged species being present in it, the likelihood for the jet to be ejected from the apex of the Taylor cone for the solution with a higher conductivity should be higher. Indeed, the PS solution in DMF, due to the higher conductivity, was more readily to spin. Further increase in both the solution viscosity and the electrostatic field strength resulted in the observed transformation from beaded to smooth fibres and the increase in the fibre size. The likely explanations are the increase in the viscoelastic force in comparison with the coulombic stretching force and the increase in the mass throughput (due to the increase in the electrostatic force) as well as the decrease in the total path length that the jet travels from the nozzle to the collector (due to the delay in the occurrence of the bending instability) [5,8]. Effects of Mixed Solvent System and Inorganic Salt Addition Due to the very high solubility of PS in DMF and the very high electro-spinnability of the resulting PS solutions in DMF, it was the most suitable choice to be used as the main solvent for preparing PS solutions in order to investigate the effects of mixed solvent system and inorganic salt addition on morphological appearance of the as-spun PS fibres. In the mixed solvents investigated, DMF was blended with DCE, EA, and MEK at a fixed volumetric ratio of 75/25 and the concentration of the resulting solutions was fixed at 30% (w/v). Figure 3 summarizes viscosity, surface tension, and conductivity of the PS solutions in DMF and the various mixed solvent systems. According to Figure 3, the addition of DCE into DMF prevealed that the resulting PS solution exhibiting the highest viscosity, followed by the PS solution in DMF, DMF/EA, and DMF/MEK, respectively. Interestingly, the surface tension of the PS solution in DMF was found to be the highest, followed by that of the solution in DMF/DCE, DMF/EA, and DMF/MEK, respectively. This is in agreement with the results summarized in Table 2, in which the property value of the PS solution in DMF was the highest, followed by that of the solution in DCE, EA, and MEK, respectively. Interestingly, the surface tension of DMF was also the highest, followed by that of DCE, EA, and MEK, respectively (Table 2). With regards to the conductivity, the PS solution in DMF exhibited the highest property value, followed by that of the solution in DMF/MEK, DMF/DCE, and DMF/EA, respectively. A good agreement with the data summarized in Table 2 is also evident, in that the property value of the PS solution in DMF was the highest, followed by that of the solution in MEK, DCE, and EA, respectively. Interestingly, the dielectric constant of DMF was the highest, followed by that of MEK, DCE, and EA, respectively (Table 1). Based on the results shown here, the properties of the solvents influence a great deal the properties of the resulting solutions. Electrospinning of these solutions was carried at a fixed elec- 350 Iranian Polymer Journal / Volume 15 Number 4 (2006)

Manee-in J. et al. Effects of Solvent Properties, Solvent System... 1000 800 600 400 200 0 50 40 30 20 10 0 without salt 1% (w/v) LiCl 1% (w/v) KCl (a) trostatic field strength of 25 kv/8.3 cm. Tables 6 shows selected SEM images of as-spun fibres from 30% (w/v) PS solutions in DMF, DMF/DCE, DMF/EA, and DMF/MEK. Only smooth fibres were observed in these images. The average size (i.e., diameter) of these fibres was also analyzed and the results are illustrated in Figure 4. Interesting to say that, the presence of minor solvents resulted in the reduction of the average diameter of the fibres which were obtained from PS solution in DMF. Specifically, the average diameter of the fibres from PS solutions in DMF/DCE, DMF/EA, and DMF/MEK was 13.2, 4.6, and 5 µm, respectively (comparing with 15.7 µm for fibres obtained from the PS solution in DMF). Finally, the effect of added electrolytes on electrospinnability of the resulting solutions and the morphological appearance of the as-spun fibres was also investigated here. In such studies, 1% (w/v) of either LiCl or KCl was added into 30% (w/v) PS solutions in DMF, DMF/DCE, DMF/EA, and DMF/MEK, respectively. Viscosity, surface tension, and conductivity of the asprepared PS solutions are also graphically summarized in Figure 3. While the addition of these inorganic salts did not alter much the surface tension of the resulting PS solutions, they did change both the viscosity and the conductivity, significantly. Specifically, both types of salts caused the viscosity of the PS solutions to without salt 1% (w/v) LiCl 1% (w/v) KCl (b) 50 2000 40 1500 30 1000 20 500 10 0 0 1% (w/v) LiCl 1% (w/v) KCl (c) Figure 3. (a) Viscosity, (b) surface tension, and (c) conductivity of 30% (w/v) PS solutions in various solvent systems with or without the addition of 1% w/v LiCl or KCl inorganic salts. without salt 1% (w/v) LiCl 1% (w/v) KCl Figure 4. Average diameter of as-spun fibers from 30% (w/v) PS solutions in various solvent systems with or without the addition of 1% w/v LiCl or KCl inorganic salts. The applied electrical field strength was 25 kv/8.3 cm. Iranian Polymer Journal / Volume 15 Number 4 (2006) 351

Effects of Solvent Properties, Solvent System... Manee-in J. et al. Table 6. Selected scanning electron micrographs (scale bar = 50 µm) of as-spun fibers from 30% (w/v) PS solutions in a mixed solvent system comprising dimethylformamide and either of 1,2-dichloroethane, ethylacetate, and methylethylketone in a fixed volumetric ratio of 75/25 with or without the addition of 1% (w/v) LiCl or KCl. The applied electrical field was 25 kv/8.3 cm. Electrostatic field strength Dimethylformamide (DMF) DMF/1,2-dichloroethane (DCE) DMF/ethylacetate (EA) DMF/methylethylketone (MEK) Neat LiCl 1% (w/v) KCl 1% (w/v) decrease in a similar extent from that of the solutions when no salts was added. Interestingly, the viscosity of the solutions containing salts showed a similar trend to that of the solutions without the salts. As expected, the addition of the inorganic electrolytes increased conductivity of the as-prepared PS solutions dramatically. Similarly, electrospinning of these solutions was carried out at a fixed electrostatic field strength of 25 kv/ 8.3 cm. Tables 6 shows selected SEM images of asspun fibres from 30% (w/v) PS solutions in DMF, DMF/DCE, DMF/EA, and DMF/MEK with the addition of either 1% (w/v) LiCl or KCl. Evidently, the obtained fibres, were smooth, but, in comparison with those obtained from the neat solutions (without the salts), the addition of these inorganic salts increased the size of the fibres, significantly. The average size of these fibres was also analyzed and the results are illustrated in Figure 4. Apparently, the addition of either type of salts resulted in a comparable increase in the average size of the resulting fibres. Specifically, an increase in the average size of the as-spun fibres of about 130, 130, 650, and 560% was observed when the either type of salts was added in the PS solutions in DMF, DMF/DCE, DMF/EA, and DMF/MEK, respectively. Since conductivity relates directly to the amount of charged species present within a volume, the marked 352 Iranian Polymer Journal / Volume 15 Number 4 (2006)

Manee-in J. et al. Effects of Solvent Properties, Solvent System... increase in the conductivity of the PS solutions upon the addition of the salts should cause both the electrostatic and the coulombic stretching forces to increase. Intuitively, the increase in the coulombic stretching force should result in the reduction in the fibre diameters (coupled with the observed reduction in the viscoelastic force with the salt addition), but the results shown in Figure 4 suggest otherwise. The likely explanations for this problem are the increase in the mass throughput (due to the increase in the electrostatic force acting on a jet segment) as well as the decrease in the total path length that the jet travels from the nozzle to the collector (due also to the increase in the electrostatic force) [5,8]. Demir et al. [12] showed that when triethylbenzyl ammonium chloride was added into polyurethaneurea solutions in DMF, a large increase in the diameters of the obtained fibres was observed, which was attributed to a dramatic increase in the mass flow and a decrease in the viscosity of the solutions. CONCLUSION The present contribution aimed at studying the effects of solvent properties, solvent system, electrostatic field strength, and inorganic salt addition on electrospinnability of the as-prepared polystyrene (PS) solutions and morphological appearance and/or size of the resulting as-spun fibres. The solvent systems under investigation were 1,2-dichloroethane (DCE), dimethylformamide (DMF), ethylacetate (EA), methylethylketone (MEK), and the blend solutions between DMF and either of DCE, EA, and MEK. Analyses of the scanning electron microscopic (SEM) images of mats of the as-spun fibres from 10% (w/v) PS solutions in various single solvents showed that the electro-spinnability of the PS solution in DMF was found to be the best, followed by those in DCE, MEK, and EA, respectively. Moreover, the electrospinnability of the PS solutions correlated well with the boiling point, dipole moment, and dielectric constant of the solvents, and the difference between the solubility parameters of the solvent and the solute, as well as with the viscosity of the resulting PS solutions. Generally, electrospinning of 10% (w/v) PS solutions resulted in the formation of beaded fibres, while electrospinning of 20 and 30% (w/v) PS solutions only resulted in the formation of smooth fibres. At 10% (w/v) of the PS solutions, with increasing electrostatic field strength (i.e., decreasing collection distance at a fixed applied potential of 25 kv or increasing applied potential at a fixed collection distance of 7 cm), the size of the beads was found to decrease and the shape of the beads appeared to be more elongated. With regards to the size of the resulting fibres, it was found that it increases with an increase in both the electrostatic field strength and the concentration of the PS solutions. Interestingly, the presence of DCE, EA, and MEK as the minor solvent (at 25 vol%) in a mixture with DMF reduced the size of the obtained fibres. Finally, incorporation of LiCl and KCl to modify the conductivity of the PS solutions caused the size of the fibres to increase appreciably. ACKNOWLEDGMENT This work was supported in part by (1) the National Research Council of Thailand (NRCT), (2) The Thailand Research Fund (through a Master Research Grants program: TRF-MRG), (3) The Petroleum and Petrochemical Technology Consortium [through a Thai governmental loan from the Asian Development Bank (ADB)], and (4) The Petroleum and Petrochemical College (PPC), Chulalongkorn University. REFERENCES 1. Huang Z.M., Zhang Y.Z., Kotaki M., Ramakrishna S., A review on polymer nanofibres by electrospinning and their applications in nanocomposites, Compos. Sci. Technol., 63, 2223-2253, 2003. 2. ISI Web of Science: http://portal15.isiknowledge.com 3. Reneker D.H., Yarin A.L., Fong H., Koombhongse S., Bending instability of electrically charged liquid jets of polymer solutions in electrospinning, J. Appl. Phys., 87, 4531-4547, 2000. 4. Deitzel J.M., Kleinmeyer J.D., Hirvonen J.K., Tan N.C.B., Controlled deposition of electrospun poly(ethylene oxide) fibres, Polymer, 42, 8163-8170, 2001. 5. Mit-uppatham C., Nithitanakul M., Supaphol P., Ultrafine electrospun polyamide-6 fibres: Effect of solution condi- Iranian Polymer Journal / Volume 15 Number 4 (2006) 353

Effects of Solvent Properties, Solvent System... Manee-in J. et al. tions on morphology and average fibre diameter, Macromol. Chem. Phys., 205, 2327-2338, 2004. 6. Doshi J., Reneker D.H., Electrospinning process and applications of electrospun fibres, J. Electrostatics, 35, 151-160, 1995. 7. Baumgarten P.K., Electrostatic spinning of acrylic microfibres, J. Colloid. Interf. Sci., 36, 71-79, 1971. 8. Wannatong L., Sirivat A., Supaphol P., Effects of solvents on electrospun polymeric fibres: Preliminary study on polystyrene, Polym. Int., 53, 1851-1859, 2004. 9. Jarusuwannapoom T., Hongroijanawiwat W., Jitjaicham S., Wannatong L., Nithitanakul M., Pattamaprom C., Koombhongse P., Rangkupan R., Supaphol P., Effect of solvents on electro-spinnability of polystyrene solutions and morphological appearance of resulting electrospun polystyrene fibres, Eur. Polym. J., 41, 409-421, 2005. 10. Wutticharoenmongkol P., Supaphol P., Srikhirin T., Kerdcharoen T., Osotchan T., Electrospinning of polystyrene/ poly(2-methoxy-5-(2 -ethylhexyloxy)-1,4-phenylene vinylene) blends, J. Polym. Sci. B: Polym. Phys., 43, 1881-1891, 2005. 11. Zuo W., Zhu M., Yang W., Yu H., Chen Y., Zhang Y., Experimental study on relationship between jet instability and formation of beaded fibres during electrospinning, Polym. Eng. Sci., 45, 704-709, 2005. 12. Demir M.M., Yilgor I., Yilgor E., Erman B., Electrospinning of polyurethane fibres, Polymer, 43, 3303-3309, 2002. 354 Iranian Polymer Journal / Volume 15 Number 4 (2006)